CN110849502A - Preparation method of tetramethoxyphenyl zirconium porphyrin nanotube-selenium trioxide nanosheet composite thermosensitive sensing material - Google Patents
Preparation method of tetramethoxyphenyl zirconium porphyrin nanotube-selenium trioxide nanosheet composite thermosensitive sensing material Download PDFInfo
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Abstract
The invention relates to the field of thermosensitive sensing materials, and discloses a preparation method of a tetramethoxyphenyl zirconium porphyrin nanotube-selenium trioxide nanosheet composite thermosensitive sensing material, which comprises the steps of firstly preparing tetramethoxyphenyl benzaldehyde, and reacting the tetramethoxyphenyl benzaldehyde with trichloromethane under hydrogen chloride atmosphere to prepare tetramethoxyphenyl porphyrin; adding tetramethoxyphenyl porphyrin and anhydrous zirconium chloride into a mixed solution of benzoic acid and polyethylene glycol for reaction to obtain tetramethoxyphenyl zirconium porphyrin; selenium trioxide is prepared, selenium trioxide nanosheets are generated on the stems of the tetramethoxyphenyl zirconium porphyrin nanotubes by a hydrothermal method, and a polymethylphenylsiloxane film is spin-coated on the surfaces of the tetramethoxyphenyl zirconium porphyrin nanotubes and the selenium trioxide nanosheets, so that the structural regularity of the tetramethoxyphenyl zirconium porphyrin nanotubes and selenium trioxide nanosheets composite material is ensured, and meanwhile, a certain protection effect is achieved on the material.
Description
Technical Field
The invention relates to the field of thermosensitive sensing materials, in particular to a preparation method of a tetramethoxyphenyl zirconium porphyrin nanotube-selenium trioxide nanosheet composite thermosensitive sensing material.
Background
Porphyrins are compounds with large pi structures with bionic properties of a plurality of important enzyme activity points, are active centers of a plurality of proteins and enzymes in the nature, and are widely researched in various fields due to unique structures and superior properties. Many porphyrins exist in nature in a form of being matched with metal ions, and porphyrin or modified porphyrin can be coordinated with metals such as iron, cobalt, aluminum and the like, so that the copolymerization of carbon dioxide and epoxy compounds is catalyzed under the combined action of a cocatalyst. The porphyrin nanotube has large specific surface area, and can enhance electric signals and improve catalytic capability. In living bodies, porphyrins are often present in a water-soluble form, and water-soluble porphyrins can also be used as DNA removal catalysts, photodynamic therapy heat-sensitive agents, wastewater treatment catalysts, gas detectors, and the like.
Selenium trioxide is a colorless crystalline chemical substance, which is easily hygroscopic in air. Selenium trioxide is a transition metal oxide, has a layered structure which is kept together by weak van der waals force and abundant active edge sites, is used as a semiconductor photoelectric material, and dangling bonds and adsorption on the surface of a selenium trioxide nanosheet can form defects and capture states and can capture electrons and holes, so that the selenium trioxide has wide application prospects in the aspects of light absorption, photoluminescence, photoelectric conversion, photocatalysis, sensors and the like.
However, there are few reports on the use of the composite materials as sensor materials, and therefore, research on the direction has certain significance in the field of sensor materials.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a tetramethoxyphenyl zirconium porphyrin nanotube-selenium trioxide nanosheet composite thermosensitive sensing material, which comprises the steps of firstly preparing tetramethoxyphenyl benzaldehyde, and reacting the tetramethoxyphenyl benzaldehyde with trichloromethane under hydrogen chloride atmosphere to prepare tetramethoxyphenyl porphyrin; adding tetramethoxyphenyl porphyrin and anhydrous zirconium chloride into a mixed solution of benzoic acid and polyethylene glycol for reaction to obtain tetramethoxyphenyl zirconium porphyrin; selenium trioxide is prepared, selenium trioxide nanosheets are generated on the stems of the tetramethoxyphenyl zirconium porphyrin nanotubes by a hydrothermal method, and a polymethylphenylsiloxane film is spin-coated on the surfaces of the tetramethoxyphenyl zirconium porphyrin nanotubes and the selenium trioxide nanosheets, so that the structural regularity of the tetramethoxyphenyl zirconium porphyrin nanotubes and selenium trioxide nanosheets composite material is ensured, and meanwhile, a certain protection effect is achieved on the material.
The specific technical scheme of the invention is as follows: a preparation method of a tetramethoxyphenyl zirconium porphyrin nanotube-selenium trioxide nanosheet composite thermosensitive sensing material comprises the following steps:
step 1: preparation of tetramethoxybenzaldehyde: adding p-hydroxybenzaldehyde and distilled water into a container filled with NaOH aqueous solution, adding dimethyl sulfate and tetrabutylammonium bromide after the p-hydroxybenzaldehyde is completely dissolved, and heating and refluxing for reaction; after the reaction liquid is cooled, washing with alkali liquor until the pH value is 7.5-8.5; drying the obtained product, distilling in vacuum, collecting the obtained product, and storing for later use.
Step 2: preparation of tetramethoxyphenyl porphyrin: dissolving the tetramethoxybenzaldehyde in xylene and dichloromethane, reacting with dichloromethane dissolved with fuming sulfuric acid under hydrogen chloride atmosphere, and stirring and refluxing at 120-150 ℃ for 3-5 h; and then cooling the reaction liquid, placing the reaction liquid in absolute ethyl alcohol, standing overnight at room temperature, performing suction filtration, washing to obtain crude tetramethoxyphenyl porphyrin, purifying to obtain tetramethoxyphenyl porphyrin, and storing for later use.
And step 3: preparation of tetramethoxyphenyl zirconium porphyrin: preparation of tetramethoxyphenyl zirconium porphyrin: adding a mixed solution of tetramethoxyphenyl porphyrin, benzoic acid, polyethylene glycol and anhydrous zirconium chloride into a container containing N, N-diethylformamide at the temperature of 100 ℃ and 120 ℃, reacting for 5-10h under an inert gas atmosphere, cooling to room temperature, pouring into water, standing for precipitation, filtering, washing to obtain crude tetramethoxyphenyl zirconium porphyrin, and purifying to obtain the tetramethoxyphenyl zirconium porphyrin.
And 4, step 4: preparing tetramethoxyphenyl zirconium porphyrin nanotubes: and immersing the pretreated porous carbon nanotube substrate into a mixed solution of tetramethoxyphenyl zirconium porphyrin and propylene oxide, and then drying to form the tetramethoxyphenyl zirconium porphyrin nanotube growing on the porous carbon nanotube substrate.
And 5: preparing selenium trioxide: at the temperature of 65-75 ℃, potassium selenate is refluxed in excessive sulfur trioxide until salt is completely dissolved and two liquid layers are formed, the upper layer is a mixture of sulfur trioxide and selenium trioxide, the upper layer liquid is poured out, sulfur trioxide is evaporated from the mixture to obtain selenium trioxide, and the selenium trioxide is subjected to vacuum sublimation at the temperature of 110-130 ℃ to obtain purified selenium trioxide.
Step 6: preparing a tetramethoxyphenyl zirconium porphyrin-selenium trioxide composite material: and (3) stirring and reacting the selenium trioxide obtained in the step (6), deionized water and the tetramethoxyphenyl zirconium porphyrin nanotube growing on the porous carbon nanotube substrate in a polytetrafluoroethylene reaction kettle at 140 ℃ and 160 ℃ for 30-40h, centrifuging, washing and drying to obtain the tetramethoxyphenyl zirconium porphyrin-selenium trioxide nanosheet composite material.
And 7: preparing a tetramethoxyphenyl zirconium porphyrin nanotube-selenium trioxide nanosheet composite thermosensitive sensing material: putting the tetramethoxyphenyl zirconium porphyrin-selenium trioxide composite material into a spin coater, spin-coating polymethylphenylsiloxane, and drying to obtain the tetramethoxyphenyl zirconium porphyrin nanotube-selenium trioxide nanosheet composite thermosensitive sensing material.
The invention firstly prepares the tetramethoxyphenyl benzaldehyde, and the tetramethoxyphenyl porphyrin is prepared by reacting the tetramethoxyphenyl benzaldehyde with dichloromethane in hydrogen chloride atmosphere; adding tetramethoxyphenyl porphyrin and anhydrous zirconium chloride into a mixed solution of benzoic acid and polyethylene glycol for reaction to obtain tetramethoxyphenyl zirconium porphyrin; selenium trioxide is prepared, a hydrothermal method is utilized to enable the tetramethoxyphenyl zirconium porphyrin nanotube stem to generate selenium trioxide nanosheets, and a polymethylphenylsiloxane film is coated on the surfaces of the tetramethoxyphenyl zirconium porphyrin nanotube-selenium trioxide nanosheets in a spin mode, so that the structural regularity of the tetramethoxyphenyl zirconium porphyrin nanotube-selenium trioxide nanosheet composite material is guaranteed, and meanwhile, a certain protection effect is achieved on the material.
Preferably, in the step 4, the adding amount of tetramethoxyphenyl zirconium porphyrin and the adding amount of propylene oxide are respectively 30-80mg and 20-50mL, and the tetramethoxyphenyl zirconium porphyrin and the propylene oxide are mixed and stirred for 10-25 min; the soaking time of the porous carbon nanotube substrate is 7-10 h; the reaction product is dried in vacuum at 75-85 ℃ for 4-8 h.
Preferably, in step 4, the preparation method of the porous carbon nanotube substrate comprises: putting the porcelain boat containing 180-220mg ferrocene into a quartz tube, putting the quartz tube into a program control heating furnace, and introducing Ar gas to discharge air in the tube before reaction so as to prevent the ferrocene from being oxidized; rapidly raising the temperature in the tube to 350-450 ℃ at the speed of 10-20 ℃/min, and sublimating the ferrocene; then introducing Ar gas at the speed of 180-220mL/min and raising the temperature in the tube to 1000-1400 ℃; then, C is introduced at 8-12mL/min2H4And continuously introducing Ar gas; reacting at 14000 ℃ for 25-35 min; and turning off the power supply to naturally cool the carbon nanotube to room temperature to obtain the porous carbon nanotube.
Preferably, in step 4, the pretreatment of the porous carbon nanotube substrate is high-temperature roasting, specifically as follows: taking a porous carbon nanotube with the outer diameter of 5-7mm, the inner diameter of 3-5mm and the average aperture of 140-160nm as a substrate, cutting the tube into the length of 45-55mm, sequentially soaking the tube in 25-35mL of deionized water, methanol, ether and acetone solvents, and putting the tube into an ultrasonic water bath for cleaning; after 25-35min, the porous carbon nanotube substrate is placed in a vacuum drying oven at 75-85 ℃ for 6-10h, then calcined at 450-550 ℃ for 4-6h, and the outer surface of the substrate is wrapped by a polytetrafluoroethylene tape, weighed and stored for later use.
Preferably, in step 7, the drying temperature is 75-85 ℃ and the drying time is 4-6 h.
Preferably, step 1 is specifically: adding 10-30g of p-hydroxybenzaldehyde and 180mL of 100-180mL of distilled water into a container filled with NaOH aqueous solution, stirring for 3-7min until the p-hydroxybenzaldehyde is completely dissolved, adding 15-25mL of dimethyl sulfate and 2.5-3.5g of tetrabutylammonium bromide, heating for reflux reaction, cooling the reaction solution, and washing with alkali liquor until the pH value is 7.5-8.5; vacuum drying at 55-65 deg.C for 3-7h, drying the obtained product, vacuum distilling, collecting the obtained product, and storing for use.
Preferably, in step 1, the concentration of the NaOH aqueous solution is 20-30 wt%; the reaction temperature range is 80-150 ℃, and the reflux time is 5-10 h; when the temperature is reduced to 100 ℃, the reaction liquid is quickly transferred and gradually cooled to room temperature, and after the reaction liquid is cooled, the reaction liquid is washed by alkali liquor until the pH value is 8.
Preferably, in step 2, the purification manner is to adjust pH, and specifically, the following steps are performed: dissolving crude tetramethoxyphenyl porphyrin in deionized water, adding anhydrous sodium carbonate to adjust pH to 11.5-12.5, filtering, concentrating the filtrate on a water vapor bath until the filtrate is dry, then adjusting pH to 3.5-5.5 with dilute hydrochloric acid with the mass fraction of 4-8%, filtering, concentrating the filtrate on a water vapor bath until the filtrate is dry, repeating the steps for multiple times, extracting the filtrate for multiple times by using n-butanol when the pH is 5.5-6.5, standing for 4-6h for liquid separation, taking an upper n-butanol layer, and performing vacuum rotary evaporation to obtain tetramethoxyphenyl porphyrin, and storing for later use.
Preferably, in step 3, the addition amount of tetramethoxyphenylporphyrin is 60-100mg and the addition amount of anhydrous zirconium chloride is 60-100mg in mg and mL; the addition amount of the N, N-diethylformamide is 90-150mL, and the addition amount of the deionized water is 60-150 mL.
Preferably, in step 3, inert gas is introduced for 5-10min before the reaction starts; standing for 1-5 h.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, a layer of compact tetramethoxyphenyl zirconium porphyrin nanotube with highly regular orientation is grown on the porous carbon nanotube substrate, and the formation of the structure enlarges the active range of electrons, and is beneficial to improving the transmission efficiency of the electrons;
2. the tetramethoxyphenyl zirconium porphyrin nanotube-selenium trioxide nanosheet composite thermosensitive sensing material formed by the invention is beneficial to enlarging the specific surface area, improving the sensitivity of the sensor and increasing the transmission path of electrons;
3. according to the invention, the polymethylphenylsiloxane nano-film is utilized, so that the tetramethoxyphenyl zirconium porphyrin nano-tube-selenium trioxide nano-sheet composite thermosensitive sensing material has a more regular structure, the stability of the sensing material is improved, the electronic transfer is facilitated, and the conduction efficiency of the sensor is improved.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
1) Preparation of tetramethoxybenzaldehyde
30g of p-hydroxybenzaldehyde and 160mL of distilled water are added into a 250mL three-necked bottle filled with 25 wt% of NaOH aqueous solution, and after the p-hydroxybenzaldehyde is completely dissolved, 5g of dimethyl sulfate and 10g of tetrabutylammonium bromide (Bu) are added4NBr) at 100 ℃ for 7 h. When the temperature is reduced to 100 ℃, the reaction solution is quickly transferred to a big beaker, is gradually cooled to room temperature, and is washed with NaOH aqueous solution for three times after the reaction solution is cooled until the pH value is 8. Drying in a vacuum oven at 60 ℃ for 5h to obtain a crude product; drying the obtained product, then carrying out vacuum distillation, collecting the obtained product, and storing the product for later use.
2) Preparation of tetramethoxyphenylporphyrins
Dissolving 40g of tetramethoxybenzaldehyde in 180mL of toluene and dichloromethane, reacting with dichloromethane dissolved with fuming sulfuric acid under hydrogen chloride atmosphere, and stirring and refluxing for 3h at 120 ℃; then cooling the reaction liquid, placing the reaction liquid in absolute ethyl alcohol, standing overnight at room temperature, performing suction filtration, washing to obtain 73g of crude tetramethoxyphenyl porphyrin, and purifying: dissolving crude tetramethoxyphenyl porphyrin in 100mL of deionized water, adding anhydrous sodium carbonate to adjust pH to 12, filtering, concentrating the filtrate on a water vapor bath until the filtrate is dry, then adjusting pH to 4 with 6% dilute hydrochloric acid by mass fraction, filtering, concentrating the filtrate on a water vapor bath until the filtrate is dry, repeating the steps for 3 times, extracting 5 times with n-butanol when the pH is 6, standing for 5h for liquid separation, taking an upper n-butanol layer, performing vacuum rotary evaporation to obtain tetramethoxyphenyl porphyrin, and storing for later use.
3) Preparation of tetramethoxyphenyl zirconium porphyrin
At 120 ℃, adding a mixed solution of 90mLN, N-diethylformamide, 60mg benzoic acid and 80mL polyethylene glycol into a 250mL three-neck flask, adding 60mg tetramethoxyphenyl porphyrin and 70mg anhydrous zirconium chloride into the three-neck flask, and introducing nitrogen for 5min before the reaction starts; keeping the temperature at 150 ℃ in the nitrogen atmosphere for reaction for 10h, cooling to room temperature, pouring into water, standing for precipitation for 4h, filtering, washing to obtain crude tetramethoxyphenyl zirconium porphyrin, and purifying to obtain tetramethoxyphenyl zirconium porphyrin.
4) Preparation of porous carbon nanotube substrate
The porcelain boat containing 200mg of ferrocene is placed into a quartz tube, then the quartz tube is placed into a program control heating furnace, and Ar gas is introduced to discharge air in the tube before reaction so as to prevent the ferrocene from being oxidized. Rapidly raising the temperature in the tube to 400 ℃ at the speed of 15 ℃/min to sublimate the ferrocene; then, Ar gas was introduced at 200mL/min and the temperature in the tube was raised to 1200 ℃. At this time, C was introduced at a rate of 10mL/min2H4And continuously introducing Ar gas; reacting at 1200 ℃ for 30 min; and turning off the power supply to naturally cool the carbon nanotube to room temperature to obtain the porous carbon nanotube.
The pretreatment process comprises the following steps: taking a porous carbon nanotube with 6mm outer diameter, 4mm inner diameter and 150nm average pore diameter as a substrate, cutting the tube into 50mm length, sequentially soaking in 30mL deionized water, methanol, ether and acetone solvents, and putting into an ultrasonic water bath for cleaning; and after 30min, drying the porous carbon nanotube substrate in a vacuum drying oven at 80 ℃ for 8h, calcining at 500 ℃ for 5h, wrapping the outer surface of the substrate with a polytetrafluoroethylene tape, weighing, and storing for later use.
5) Preparation of tetramethoxyphenyl zirconium porphyrin nanotube
Adding 30mg of tetramethoxyphenyl zirconium porphyrin into 15mL of propylene oxide solution, magnetically stirring for 10min until the solution is clear and transparent, immersing the porous carbon nanotube substrate into the tetramethoxyphenyl zirconium porphyrin-propylene oxide mixed solution for 9h, taking out, and drying the reaction product in a vacuum drying oven at 80 ℃ for 10h to obtain the tetramethoxyphenyl zirconium porphyrin nanotube growing on the porous carbon nanotube substrate.
6) Preparation of selenium trioxide
Refluxing 50mg potassium selenate in sulfur trioxide at a flow rate of 10mL/min at 70 deg.C until the salt is completely dissolved and two liquid layers are formed, the upper layer is a mixture of sulfur trioxide and selenium trioxide, decanting the upper layer liquid, evaporating sulfur trioxide from the mixture to obtain selenium trioxide, and treating SeO at 120 deg.C3Vacuum sublimation can be carried out to purify the product.
7) Preparation of tetramethoxyphenyl zirconium porphyrin-selenium trioxide composite material
Putting 5mg of selenium trioxide, 10mL of deionized water and 60mg of tetramethoxyphenyl zirconium porphyrin nanotube into a polytetrafluoroethylene reaction kettle, stirring and reacting for 40h at 140 ℃, centrifuging the obtained product for 10min at the rotating speed of 5000r by using a centrifuge, collecting the product, washing the product for 5 times by using water and absolute ethyl alcohol respectively, putting the product into a vacuum drying oven, and drying the product for 10h at 80 ℃ to obtain the tetramethoxyphenyl zirconium porphyrin-selenium trioxide nanosheet composite material.
8) Preparation of tetramethoxyphenyl zirconium porphyrin-selenium trioxide-polymethylphenylsiloxane composite material
Putting 10mg of tetramethoxyphenyl zirconium porphyrin-selenium trioxide composite material into a spin coater, spin-coating 3 mu L of polymethylphenyl siloxane, putting the spin-coated tetramethoxyphenyl zirconium porphyrin-selenium trioxide composite material into a vacuum drying oven, and drying for 5h at 60 ℃ to obtain the tetramethoxyphenyl zirconium porphyrin-selenium trioxide nanosheet-polymethylphenyl siloxane composite thermosensitive sensing material.
The method comprises the steps of averagely dividing 60mg of tetramethoxyphenyl zirconium porphyrin-selenium trioxide nanosheets-polymethylphenylsiloxane composite thermosensitive sensing materials into 5 parts, respectively placing the 5 parts in a beaker, placing the beaker in a constant-temperature water bath kettle, adjusting the temperature to be 10 ℃, 30 ℃, 50 ℃, 80 and 100 ℃, placing the beaker for 3min under the water bath condition, and measuring the temperature of the material by using a thermometer to obtain the temperature of 9 ℃, 28 ℃, 48, 76 and 95 ℃. Therefore, the tetramethoxyphenyl zirconium porphyrin-selenium trioxide nanosheet-polymethylphenylsiloxane composite thermosensitive sensing material has a good sensing effect.
Example 2
1) Preparation of tetramethoxybenzaldehyde
15g of p-hydroxybenzaldehyde and 100mL of distilled water were taken and added to a 250mL three-necked flask containing an aqueous solution of 20 wt% NaOH, and 7g of dimethyl sulfate and 9g of tetrabutylammonium bromide (Bu) were added after p-hydroxybenzaldehyde was completely dissolved4NBr) at 120 ℃ for 7 h. When the temperature is reduced to 100 ℃, the reaction solution is quickly transferred to a big beaker, is gradually cooled to room temperature, and is washed with NaOH aqueous solution for three times after the reaction solution is cooled until the pH value is 8. Drying in a vacuum oven at 60 deg.C for 5h to obtainA crude product; drying the obtained product, then carrying out vacuum distillation, collecting the obtained product, and storing the product for later use.
2) Preparation of tetramethoxyphenylporphyrins
Dissolving 60g of tetramethoxybenzaldehyde in 180mL of toluene and chloroform, reacting with the chloroform dissolved with fuming sulfuric acid under hydrogen chloride atmosphere, and stirring and refluxing for 4.5h at 135 ℃; then cooling the reaction liquid, placing the reaction liquid in absolute ethyl alcohol, standing overnight at room temperature, performing suction filtration, washing to obtain 95g of crude tetramethoxyphenyl porphyrin, and purifying: dissolving crude tetramethoxyphenyl porphyrin in 100mL of deionized water, adding anhydrous sodium carbonate to adjust pH to 12, filtering, concentrating the filtrate on a water vapor bath until the filtrate is dry, then adjusting pH to 4 with 6% dilute hydrochloric acid by mass fraction, filtering, concentrating the filtrate on a water vapor bath until the filtrate is dry, repeating the steps for 3 times, extracting 5 times with n-butanol when the pH is 6, standing for 5h for liquid separation, taking an upper n-butanol layer, performing vacuum rotary evaporation to obtain tetramethoxyphenyl porphyrin, and storing for later use.
3) Preparation of tetramethoxyphenyl zirconium porphyrin
At 100 ℃, adding a mixed solution of 60mL of N, N-diethylformamide, 80mg of benzoic acid and 100mL of polyethylene glycol into a 250mL three-neck flask, adding 80mg of tetramethoxyphenyl porphyrin and 85mg of anhydrous zirconium chloride into the three-neck flask, and introducing nitrogen for 10min before the reaction starts; keeping the temperature at 120 ℃ in the nitrogen atmosphere for reacting for 8h, cooling to room temperature, pouring into water, standing for precipitating for 5h, filtering, washing to obtain crude tetramethoxyphenyl zirconium porphyrin, and purifying to obtain tetramethoxyphenyl zirconium porphyrin.
4) Preparation of porous carbon nanotube substrate
The porcelain boat containing 200mg of ferrocene is placed into a quartz tube, then the quartz tube is placed into a program control heating furnace, and Ar gas is introduced to discharge air in the tube before reaction so as to prevent the ferrocene from being oxidized. Rapidly raising the temperature in the tube to 400 ℃ at the speed of 15 ℃/min to sublimate the ferrocene; then, Ar gas was introduced at 200mL/min and the temperature in the tube was raised to 1200 ℃. At this time, C was introduced at a rate of 10mL/min2H4And continuously introducing Ar gas; reacting at 1200 ℃ for 30 min; turning off the power supply to cool it naturally to roomAnd finally obtaining the porous carbon nanotube.
The pretreatment process comprises the following steps: taking a porous carbon nanotube with 6mm outer diameter, 4mm inner diameter and 150nm average pore diameter as a substrate, cutting the tube into 50mm length, sequentially soaking in 30mL deionized water, methanol, ether and acetone solvents, and putting into an ultrasonic water bath for cleaning; and after 30min, drying the porous carbon nanotube substrate in a vacuum drying oven at 80 ℃ for 8h, calcining at 500 ℃ for 5h, wrapping the outer surface of the substrate with a polytetrafluoroethylene tape, weighing, and storing for later use.
5) Preparation of tetramethoxyphenyl zirconium porphyrin nanotube
Adding 40mg of tetramethoxyphenyl zirconium porphyrin into 20mL of propylene oxide solution, magnetically stirring for 15min until the solution is clear and transparent, immersing the porous carbon nanotube substrate into the tetramethoxyphenyl zirconium porphyrin-propylene oxide mixed solution for 8h, taking out, and drying the reaction product in a vacuum drying oven at 80 ℃ for 12h to obtain the tetramethoxyphenyl zirconium porphyrin nanotube growing on the porous carbon nanotube substrate.
6) Preparation of selenium trioxide
Refluxing 60mg potassium selenate in sulfur trioxide at a flow rate of 10mL/min at 80 deg.C until the salt is completely dissolved and two liquid layers are formed, the upper layer is a mixture of sulfur trioxide and selenium trioxide, decanting the upper layer liquid, evaporating sulfur trioxide from the mixture to obtain selenium trioxide, and treating SeO at 125 deg.C3Vacuum sublimation can be carried out to purify the product.
7) Preparation of tetramethoxyphenyl zirconium porphyrin-selenium trioxide composite material
Putting 8mg of selenium trioxide, 15mL of deionized water and 80mg of tetramethoxyphenyl zirconium porphyrin nanotube into a polytetrafluoroethylene reaction kettle, stirring and reacting for 35h at 150 ℃, centrifuging the obtained product for 10min at the rotating speed of 4000r by using a centrifuge, collecting the product, washing the product for 4 times by using water and absolute ethyl alcohol respectively, putting the product into a vacuum drying oven, and drying the product for 10h at 80 ℃ to obtain the tetramethoxyphenyl zirconium porphyrin-selenium trioxide nanosheet composite material.
8) Preparation of tetramethoxyphenyl zirconium porphyrin-selenium trioxide-polymethylphenylsiloxane composite material
Placing 20mg of tetramethoxyphenyl zirconium porphyrin-selenium trioxide composite material in a spin coater, spin-coating 5 mu L of polymethylphenyl siloxane, placing the spin-coated tetramethoxyphenyl zirconium porphyrin-selenium trioxide composite material in a vacuum drying oven, and drying for 8h at 100 ℃ to obtain the tetramethoxyphenyl zirconium porphyrin-selenium trioxide nanosheet-polymethylphenyl siloxane composite thermosensitive sensing material.
The preparation method comprises the steps of averagely dividing 90mg of tetramethoxyphenyl zirconium porphyrin-selenium trioxide nanosheets-polymethylphenylsiloxane composite thermosensitive sensing materials into 5 parts, respectively placing the 5 parts in a beaker, placing the beaker in a constant-temperature water bath kettle, adjusting the temperature to be 20 ℃, 40 ℃, 60 ℃, 80 and 100 ℃, placing the beaker for 3min under the water bath condition, and measuring the temperature of the material by using a thermometer to obtain the temperature of 18 ℃, 39 ℃, 59 ℃, 78 and 98 ℃. Therefore, the tetramethoxyphenyl zirconium porphyrin-selenium trioxide nanosheet-polymethylphenylsiloxane composite thermosensitive sensing material has a good sensing effect.
Example 3
1) Preparation of tetramethoxybenzaldehyde
Adding 20g of p-hydroxybenzaldehyde and 130mL of distilled water into a 250mL three-necked bottle filled with 30 wt% NaOH aqueous solution, and adding dimethyl sulfate and tetrabutylammonium bromide (Bu) after the p-hydroxybenzaldehyde is completely dissolved4NBr) at 150 ℃ for 5 h. When the temperature is reduced to 100 ℃, the reaction solution is quickly transferred to a big beaker, is gradually cooled to room temperature, and is washed with NaOH aqueous solution for four times after the reaction solution is cooled until the pH value is 8. Drying in a vacuum oven at 60 ℃ for 5h to obtain a crude product; drying the obtained product, then carrying out vacuum distillation, collecting the obtained product, and storing the product for later use.
2) Preparation of tetramethoxyphenylporphyrins
Dissolving 80g of tetramethoxybenzaldehyde in 200mL of methylbenzene and trichloromethane, reacting with the trichloromethane dissolved with fuming sulfuric acid under hydrogen chloride atmosphere, and stirring and refluxing for 4.5h at 135 ℃; then cooling the reaction liquid, placing the reaction liquid in absolute ethyl alcohol, standing overnight at room temperature, performing suction filtration, washing to obtain 103g of crude tetramethoxyphenyl porphyrin, and purifying: dissolving crude tetramethoxyphenyl porphyrin in 100mL of deionized water, adding anhydrous sodium carbonate to adjust pH to 12, filtering, concentrating the filtrate on a water vapor bath until the filtrate is dry, then adjusting pH to 4 with 6% dilute hydrochloric acid by mass fraction, filtering, concentrating the filtrate on a water vapor bath until the filtrate is dry, repeating the steps for 3 times, extracting 5 times with n-butanol when the pH is 6, standing for 5h for liquid separation, taking an upper n-butanol layer, performing vacuum rotary evaporation to obtain tetramethoxyphenyl porphyrin, and storing for later use.
3) Preparation of tetramethoxyphenyl zirconium porphyrin
At the temperature of 115 ℃, firstly adding a mixed solution of 50mLN, N-diethylformamide, 100mg benzoic acid and 110mL polyethylene glycol into a 250mL three-neck flask, then adding 90mg tetramethoxyphenyl porphyrin and 95mg anhydrous zirconium chloride into the three-neck flask, and introducing nitrogen for 5-min before the reaction starts; keeping the temperature at 135 ℃ in the nitrogen atmosphere for reacting for 6h, cooling to room temperature, pouring into water, standing for precipitating for 3h, filtering, washing to obtain crude tetramethoxyphenyl zirconium porphyrin, and purifying to obtain tetramethoxyphenyl zirconium porphyrin.
4) Preparation of porous carbon nanotube substrate
The porcelain boat containing 200mg of ferrocene is placed into a quartz tube, then the quartz tube is placed into a program control heating furnace, and Ar gas is introduced to discharge air in the tube before reaction so as to prevent the ferrocene from being oxidized. Rapidly raising the temperature in the tube to 400 ℃ at the speed of 15 ℃/min to sublimate the ferrocene; then, Ar gas was introduced at 200mL/min and the temperature in the tube was raised to 1200 ℃. At the moment, C2H4 is introduced at the rate of 10mL/min, and Ar gas is continuously introduced; reacting at 1200 ℃ for 30 min; and turning off the power supply to naturally cool the carbon nanotube to room temperature to obtain the porous carbon nanotube.
The pretreatment process comprises the following steps: taking a porous carbon nanotube with 6mm outer diameter, 4mm inner diameter and 150nm average pore diameter as a substrate, cutting the tube into 50mm length, sequentially soaking in 30mL deionized water, methanol, ether and acetone solvents, and putting into an ultrasonic water bath for cleaning; and after 30min, drying the porous carbon nanotube substrate in a vacuum drying oven at 80 ℃ for 8h, calcining at 500 ℃ for 5h, wrapping the outer surface of the substrate with a polytetrafluoroethylene tape, weighing, and storing for later use.
5) Preparation of tetramethoxyphenyl zirconium porphyrin nanotube
Adding 15mg of tetramethoxyphenyl zirconium porphyrin into 10mL of propylene oxide solution, magnetically stirring for 8min until the solution is clear and transparent, immersing the porous carbon nanotube substrate into the tetramethoxyphenyl zirconium porphyrin-propylene oxide mixed solution for 10h, taking out, and drying the reaction product in a vacuum drying oven at 80 ℃ for 8h to obtain the tetramethoxyphenyl zirconium porphyrin nanotube growing on the porous carbon nanotube substrate.
6) Preparation of selenium trioxide
Refluxing 30mg of potassium selenate in sulfur trioxide at a flow rate of 10mL/min at 90 ℃ until salt is completely dissolved and two liquid layers are formed, wherein the upper layer is a mixture of sulfur trioxide and selenium trioxide, pouring out the upper liquid layer, evaporating sulfur trioxide from the mixture to obtain selenium trioxide, and carrying out vacuum sublimation on SeO3 at 110 ℃ to purify the product.
7) Preparation of tetramethoxyphenyl zirconium porphyrin-selenium trioxide composite material
Putting 10mg of selenium trioxide, 15mL of deionized water and 90mg of tetramethoxyphenyl zirconium porphyrin nanotube into a polytetrafluoroethylene reaction kettle, stirring and reacting for 35h at 145 ℃, centrifuging the obtained product for 20min at 3000r by using a centrifuge, collecting the product, washing the product for 5 times by using water and absolute ethyl alcohol respectively, putting the product into a vacuum drying oven, and drying the product for 10h at 80 ℃ to obtain the tetramethoxyphenyl zirconium porphyrin-selenium trioxide nanosheet composite material.
8) Preparation of tetramethoxyphenyl zirconium porphyrin-selenium trioxide-polymethylphenylsiloxane composite material
Putting 8mg of tetramethoxyphenyl zirconium porphyrin-selenium trioxide composite material into a spin coater, spin-coating 2 mu L of polymethylphenyl siloxane, putting the spin-coated tetramethoxyphenyl zirconium porphyrin-selenium trioxide composite material into a vacuum drying oven, and drying for 12h at 80 ℃ to obtain the tetramethoxyphenyl zirconium porphyrin-selenium trioxide nanosheet-polymethylphenyl siloxane composite thermosensitive sensing material.
The method comprises the steps of averagely dividing 120mg of tetramethoxyphenyl zirconium porphyrin-selenium trioxide nanosheets-polymethylphenylsiloxane composite thermosensitive sensing materials into 5 parts, respectively placing the 5 parts in a beaker, placing the beaker in a constant-temperature water bath kettle, adjusting the temperature to be 30, 40, 50, 70 and 90 ℃, placing the beaker for 3min under the water bath condition, and measuring the temperature of the material by using a thermometer to obtain the temperature of 27, 38, 49, 68 and 89 ℃. Therefore, the tetramethoxyphenyl zirconium porphyrin-selenium trioxide nanosheet-polymethylphenylsiloxane composite thermosensitive sensing material has good sensing effect
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a tetramethoxyphenyl zirconium porphyrin nanotube-selenium trioxide nanosheet composite thermosensitive sensing material is characterized by comprising the following steps of:
step 1: preparation of tetramethoxybenzaldehyde: adding p-hydroxybenzaldehyde and distilled water into a container filled with NaOH aqueous solution, adding dimethyl sulfate and tetrabutylammonium bromide after the p-hydroxybenzaldehyde is completely dissolved, and heating and refluxing for reaction; after the reaction liquid is cooled, washing with alkali liquor until the pH value is 7.5-8.5; drying the obtained product, distilling in vacuum, collecting the product, and storing for later use;
step 2: preparation of tetramethoxyphenyl porphyrin: dissolving the tetramethoxybenzaldehyde in xylene and dichloromethane, reacting with dichloromethane dissolved with fuming sulfuric acid under hydrogen chloride atmosphere, and stirring and refluxing at 120-150 ℃ for 3-5 h; cooling the reaction liquid, placing the reaction liquid in absolute ethyl alcohol, standing overnight at room temperature, performing suction filtration, washing to obtain crude tetramethoxyphenyl porphyrin, purifying to obtain tetramethoxyphenyl porphyrin, and storing for later use;
and step 3: preparation of tetramethoxyphenyl zirconium porphyrin: preparation of tetramethoxyphenyl zirconium porphyrin: adding a mixed solution of tetramethoxyphenyl porphyrin, benzoic acid, polyethylene glycol and anhydrous zirconium chloride into a container containing N, N-diethylformamide at the temperature of 100 ℃ and 120 ℃, reacting for 5-10h under an inert gas atmosphere, cooling to room temperature, pouring into water, standing for precipitation, filtering, washing to obtain crude tetramethoxyphenyl zirconium porphyrin, and purifying to obtain the tetramethoxyphenyl zirconium porphyrin;
and 4, step 4: preparing tetramethoxyphenyl zirconium porphyrin nanotubes: immersing the pretreated porous carbon nanotube substrate into a mixed solution of tetramethoxyphenyl zirconium porphyrin and propylene oxide, and then drying to form a tetramethoxyphenyl zirconium porphyrin nanotube growing on the porous carbon nanotube substrate;
and 5: preparing selenium trioxide: refluxing potassium selenate in excessive sulfur trioxide at 65-75 ℃ until salt is completely dissolved and two liquid layers are formed, wherein the upper layer is a mixture of sulfur trioxide and selenium trioxide, pouring out the upper layer liquid, evaporating sulfur trioxide from the mixture to obtain selenium trioxide, and carrying out vacuum sublimation on the selenium trioxide at 110-130 ℃ to obtain purified selenium trioxide;
step 6: preparing a tetramethoxyphenyl zirconium porphyrin-selenium trioxide composite material: stirring the selenium trioxide obtained in the step 6, deionized water and the tetramethoxyphenyl zirconium porphyrin nanotube growing on the porous carbon nanotube substrate in a polytetrafluoroethylene reaction kettle at the temperature of 140 ℃ and 160 ℃ for reaction for 30-40h, centrifuging, washing and drying to obtain a tetramethoxyphenyl zirconium porphyrin-selenium trioxide nanosheet composite material;
and 7: preparing a tetramethoxyphenyl zirconium porphyrin nanotube-selenium trioxide nanosheet composite thermosensitive sensing material: putting the tetramethoxyphenyl zirconium porphyrin-selenium trioxide composite material into a spin coater, spin-coating polymethylphenylsiloxane, and drying to obtain the tetramethoxyphenyl zirconium porphyrin nanotube-selenium trioxide nanosheet composite thermosensitive sensing material.
2. The method according to claim 1, wherein in step 4, the amount of tetramethoxyphenyl zirconium porphyrin added is 30 to 80mg and the amount of propylene oxide added is 20 to 50mL in mg and mL, and the tetramethoxyphenyl zirconium porphyrin and the propylene oxide are mixed and stirred for 10 to 25 min; the soaking time of the porous carbon nanotube substrate is 7-10 h; the reaction product is dried in vacuum at 75-85 ℃ for 4-8 h.
3. The method according to claim 1, wherein in the step 4, the porous carbon nanotube substrate is prepared by: putting the porcelain boat containing 180-220mg ferrocene into a quartz tube, putting the quartz tube into a program control heating furnace, and introducing Ar gas to discharge air in the tube before reaction so as to prevent the ferrocene from being oxidized; rapidly raising the temperature in the tube to 350-450 ℃ at the speed of 10-20 ℃/min, and sublimating the ferrocene; then introducing Ar gas at the speed of 180-220mL/min and raising the temperature in the tube to 1000-1400 ℃; then, C is introduced at 8-12mL/min2H4And continuously introducing Ar gas; reacting at 14000 ℃ for 25-35 min; and turning off the power supply to naturally cool the carbon nanotube to room temperature to obtain the porous carbon nanotube.
4. The preparation method according to claim 1, wherein in the step 4, the pretreatment of the porous carbon nanotube substrate is high-temperature roasting, and specifically comprises the following steps: taking a porous carbon nanotube with the outer diameter of 5-7mm, the inner diameter of 3-5mm and the average aperture of 140-160nm as a substrate, cutting the tube into the length of 45-55mm, sequentially soaking the tube in 25-35mL of deionized water, methanol, ether and acetone solvents, and putting the tube into an ultrasonic water bath for cleaning; after 25-35min, the porous carbon nanotube substrate is placed in a vacuum drying oven at 75-85 ℃ for 6-10h, then calcined at 450-550 ℃ for 4-6h, and the outer surface of the substrate is wrapped by a polytetrafluoroethylene tape, weighed and stored for later use.
5. The method of claim 1, wherein in step 7, the drying temperature is 75-85 ℃ and the time is 4-6 hours.
6. The method according to claim 1, wherein step 1 comprises, in g and mL: adding 10-30g of p-hydroxybenzaldehyde and 180mL of 100-180mL of distilled water into a container filled with NaOH aqueous solution, stirring for 3-7min until the p-hydroxybenzaldehyde is completely dissolved, adding 15-25mL of dimethyl sulfate and 2.5-3.5g of tetrabutylammonium bromide, heating for reflux reaction, cooling the reaction solution, and washing with alkali liquor until the pH value is 7.5-8.5; vacuum drying at 55-65 deg.C for 3-7h, drying the obtained product, vacuum distilling, collecting the obtained product, and storing for use.
7. The method of claim 6, wherein in step 1, the concentration of the aqueous NaOH solution is 20-30 wt%; the reaction temperature range is 80-150 ℃, and the reflux time is 5-10 h; when the temperature is reduced to 100 ℃, the reaction liquid is quickly transferred and gradually cooled to room temperature, and after the reaction liquid is cooled, the reaction liquid is washed by alkali liquor until the pH value is 8.
8. The method according to claim 1, wherein in step 2, the purification is performed by adjusting the pH, and specifically comprises the following steps: dissolving crude tetramethoxyphenyl porphyrin in deionized water, adding anhydrous sodium carbonate to adjust pH to 11.5-12.5, filtering, concentrating the filtrate on a water vapor bath until the filtrate is dry, then adjusting pH to 3.5-5.5 with dilute hydrochloric acid with the mass fraction of 4-8%, filtering, concentrating the filtrate on a water vapor bath until the filtrate is dry, repeating the steps for multiple times, extracting the filtrate for multiple times by using n-butanol when the pH is 5.5-6.5, standing for 4-6h for liquid separation, taking an upper n-butanol layer, and performing vacuum rotary evaporation to obtain tetramethoxyphenyl porphyrin, and storing for later use.
9. The method according to claim 1, wherein in step 3, tetramethoxyphenylporphyrin is added in an amount of 60 to 100mg and anhydrous zirconium chloride is added in an amount of 60 to 100mg in mg and mL; the addition amount of the N, N-diethylformamide is 90-150mL, and the addition amount of the deionized water is 60-150 mL.
10. The method according to claim 1, wherein in step 3, an inert gas is introduced for 5 to 10min before the reaction starts; standing for 1-5 h.
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